CN110982052A - Titanium-based polyester for Persian and preparation method thereof - Google Patents
Titanium-based polyester for Persian and preparation method thereof Download PDFInfo
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- CN110982052A CN110982052A CN201911407273.7A CN201911407273A CN110982052A CN 110982052 A CN110982052 A CN 110982052A CN 201911407273 A CN201911407273 A CN 201911407273A CN 110982052 A CN110982052 A CN 110982052A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
Abstract
The invention relates to a titanium-based polyester for a Persian fiber and a preparation method thereof, wherein the preparation method comprises the following steps: mixing PTA, EG, SIPE, aliphatic dibasic acid and a polyester titanium catalyst composite material system, and then carrying out esterification reaction and polycondensation reaction to obtain titanium-based polyester for the Podlon, wherein the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30 and a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer; the prepared titanium-based polyester for the Polaron mainly comprises modified polyester molecular chains and a flaky titanium polyester catalyst dispersed among the modified polyester molecular chains, wherein the modified polyester molecular chains mainly comprise PTA chain segments, EG chain segments, SIPE chain segments and aliphatic binary chain segments. The method can effectively avoid agglomeration, ensure that the catalyst presents high dispersibility in the polyester synthesis process, and avoid SIPE inhibiting the activity of the catalyst; the prepared titanium-based polyester for the Posmann has excellent performance and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of polyester, and relates to a preparation method of titanium-based polyester for Persian.
Background
The Posmann (PA-B composite fiber) is a new type environment-protecting fiber for substituting acrylic fiber. The fiber combines the characteristics and advantages of various chemical fibers, has various physical indexes similar to those of acrylic fibers, has the combustion characteristics similar to those of wool, and is carbon ash after combustion. The common acrylic fiber and the blended fiber are agglomerated when the content of the acrylic fiber and the blended fiber exceeds 18 percent, the Bosslon is non-agglomerated, the elasticity is good, the woolen feeling is strong, the skin-friendly performance is superior to other fibers, the Bosslon is an environment-friendly fiber, after dyeing treatment, the dyeing reaches the European environment-friendly standard, substances harmful to skin and human bodies are not contained in the material, a plurality of side pores are separated out from the surface, and the fiber can slightly absorb moisture and perspire and is an excellent material for replacing the acrylic fiber at present.
At present, in the process of industrially synthesizing the polyester of the Poulon, more than 95 percent of heavy metal antimony catalysts are adopted, the polyester at least contains 200-450 ppm, and the consumption of the antimony catalysts for one year exceeds one million tons, thereby bringing irreversible influence on the resource consumption and the environmental pollution of the world, particularly China.
The titanium catalyst is applied to the direct esterification and continuous polycondensation polyester process, has the advantages of environmental protection, safety and high efficiency, greatly reduces the temperature in the synthesis and spinning process, reduces the energy consumption, simultaneously ensures that the physical and mechanical properties of the fiber are more uniform, improves the stability in the production process, and reduces the material.
Commercial titanium-based catalysts include two broad classes: 1) the compound/dispersion liquid of the catalyst and the glycol is in a liquid state, such as: the catalyst has poor long-term stability and dispersion performance, so that the catalyst can generate agglomeration and particle enlargement phenomena in the transportation and storage processes, can influence the catalytic activity due to hydrolysis, is easy to deteriorate, and can generate hydrolysis reaction to a greater extent at the high temperature of the synthesized polyester to destroy the catalytic activity of the catalyst; 2) the solid powder of the catalyst is introduced into a polyester synthesis system by preparing an ethylene glycol dispersion liquid during application, the catalytic activity of titanium element is generally regulated by introducing a certain proportion of Si element, and the particle size is designed to be micron-sized so as to inhibit the agglomeration of particles, but the catalyst still has the following defects: firstly, because the particle size of the solid catalyst is further increased undoubtedly when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is not good; secondly, in order to improve the dispersion effect of the solid catalyst, methods such as surface modification and the like have complex process and higher cost; thirdly, it undergoes a large degree of hydrolysis reaction at the high temperature of the synthesis of polyester to destroy the catalytic activity of the catalyst.
In addition, when the titanium-based polyester for the persilon is prepared by the traditional polymerization process, other problems exist, for example, when SIPE (sodium bis (hydroxyethyl) isophthalate-5-sulfonate) is introduced into the polyester, sulfonate ions are generated when the SIPE is ionized, and the sulfonate ions can reduce the catalytic activity of the catalyst, thereby causing adverse effects on the catalysis of the catalyst.
Therefore, the research on the titanium catalyst which has good dispersibility, can be added before or after the esterification reaction and is not easily influenced by SIPE has very important significance on the method for preparing the titanium-based polyester for the Bosman.
Disclosure of Invention
The invention aims to solve the problems that polyester catalysts in the prior art are poor in dispersity and can only be added in a polycondensation reaction stage and SIPE is introduced to inhibit the activity of the catalysts, and provides a preparation method of titanium-based polyester for Podlan, wherein the catalyst is wrapped by a polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided, the influence of SIPE on the catalyst is avoided, and the catalyst is ensured to have higher catalytic activity; the catalyst is a sheet titanium polyester catalyst, can be added before esterification reaction or after esterification reaction, and can solve the problem of poor dispersibility while exerting esterification catalysis and polycondensation catalysis.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of titanium-based polyester for Posdon comprises mixing PTA, EG, SIPE, aliphatic dibasic acid and polyester titanium catalyst composite material system, and performing esterification reaction and polycondensation reaction to obtain titanium-based polyester for Posdon;
the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30 and a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer.
When the titanium-based polyester for the Persian is prepared by adopting the traditional polymerization process, the catalyst is easy to agglomerate before being added into a reaction kettle due to poor dispersion performance, so that the catalytic activity is influenced, and the catalyst is easy to deteriorate, in order to avoid the agglomeration of the catalyst, the generally adopted method is to regulate the catalytic activity of the titanium element by introducing a certain proportion of Si element, and the particle size is designed to be micron-sized so as to inhibit the agglomeration of particles, but the methods have the following problems:
1) because the particle size of the solid catalyst is undoubtedly further increased when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is poor; 2) in order to improve the dispersion effect of the solid catalyst, methods such as surface modification and the like have complex process and higher cost; 3) the catalyst can generate hydrolysis reaction to a large extent at high temperature for synthesizing polyester so as to destroy the catalytic activity of the catalyst;
the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided, the problems are solved, the polyester prepolymer has a high melting point, and only melts at a high temperature to release the catalyst in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided, and meanwhile, the polyester prepolymer is an intermediate for preparing a polyester high polymer and has excellent intrinsic compatibility with an intermediate system for synthesizing the high polymer, so that the polyester prepolymer can show high dispersibility in the polyester synthesis process;
when the titanium-based polyester for the Persian is prepared by adopting a traditional polymerization process, SIPE is introduced into the polyester, the SIPE can be ionized to generate sulfonate ions, and the sulfonate ions can react with a titanium catalyst to further generate adverse effects on the activity of the catalyst;
in addition, when the polyester is prepared by adopting the traditional polymerization process, the catalyst is generally added into a pre-polycondensation kettle after the esterification reaction is finished, the main reason is that the catalyst is easy to hydrolyze under the action of the high-temperature esterification reaction and water generated by the high-temperature esterification reaction to reduce or even lose the catalytic activity, however, the catalyst also has the esterification catalytic action although mainly exerting the polycondensation catalytic action, and the catalyst cannot exert the esterification catalytic action and cannot fully exert the effect of the catalyst after the esterification reaction is finished;
the catalyst can be added before the esterification reaction or after the esterification reaction, can play roles of esterification catalysis and polycondensation catalysis, and has the main reason that the catalyst is a sheet-shaped titanium polyester catalyst which has excellent hydrolysis resistance, and a polyester prepolymer with the polymerization degree of 5-30 serving as a load substrate can avoid the agglomeration of the catalyst before the polyester prepolymer is added into a polymerization system, so that the problem of poor dispersibility is solved, and the catalyst can be melted in the esterification reaction process to release the catalyst so as to enable the polyester prepolymer to play roles of esterification catalysis.
As a preferred technical scheme:
the preparation method of the titanium-based polyester for the Persian comprises the following specific steps:
(1) mixing PTA, EG and a polyester titanium catalyst composite material system, and then carrying out esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 200-300 KPa, the temperature is 245-255 ℃, and the time is 3-4 h; the temperature of the esterification reaction in the traditional process is generally 260-270 ℃, the temperature of the esterification reaction is lower and is 245-255 ℃, and the main reason is that on the premise of better mass transfer conditions, the high activity of the titanium catalyst can be fully exerted, the esterification speed is higher, so the required esterification reaction temperature is relatively lower;
(2) carrying out copolymerization modification on the esterified oligomer, SIPE and aliphatic dibasic acid to obtain a copolymerization modified esterified substance, wherein the reaction pressure is 10-100 KPa, the temperature is 230-250 ℃, and the reaction time is 1-1.5 h;
(3) pre-polycondensation reaction is carried out on the copolymerization modified esterified product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 1-2 KPa, the temperature is 250-260 ℃, and the time is 0.5-1 h;
(4) carrying out final polycondensation on the pre-polycondensation product to obtain a titanium-based polyester melt for the Podlon, wherein the pressure of the final polycondensation reaction is 50-100 Pa, the temperature is 260-270 ℃, and the time is 1.5-2.5 h;
(5) and cooling and dicing the polyester melt with the titanium-based polyester to obtain the polyester chips with the titanium-based polyester for the polystyrene.
According to the preparation method of the titanium-based polyester for the Poslon, in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium-based polyester catalyst contained in the polyester titanium-based catalyst composite material system in the esterification reaction process is 8-13 ppm of the theoretical mass of the titanium-based polyester for the Poslon based on the mass of the titanium element; in the traditional process, the addition amount of the titanium catalyst is about 20ppm of the theoretical mass of the titanium-based polyester for the Posman due to the problems of dispersibility and non-hydrolysis resistance and the existence of sulfonic acid groups in the SIPE, and the comparison shows that the addition amount of the catalyst is obviously reduced, and the main reason is that the polyester titanium catalyst composite material can be only melted at a higher temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation process can be reduced and even avoided;
in the step (2), the addition amount of SIPE is 50-70 wt% of the addition amount of EG in the step (1), the addition amount of aliphatic dibasic acid is 3-5 wt% of the addition amount of EG in the step (1), and the aliphatic dibasic acid is more than one of oxalic acid, malonic acid, succinic acid, adipic acid and sebacic acid;
in the step (4), the intrinsic viscosity of the titanium-based polyester melt for the Possian is 0.38-0.40 dL/g, the chroma L value of the titanium-based polyester for the Possian obtained by sampling from the titanium-based polyester melt for the Possian is 88-90, and the b value is 5-6.
According to the preparation method of the titanium-based polyester for the Posdon, the polyester prepolymer also contains the stabilizer and the toner, the mass contents of the sheet-shaped titanium-based polyester catalyst, the stabilizer and the toner in the polyester titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%, the stabilizer and the toner are not required to be added and can be not added, and the stabilizer is generally added after the esterification reaction and before the pre-polycondensation reaction when the polyester is synthesized by adopting the traditional process.
The preparation method of the titanium-based polyester for the Persian adopts the structural general formula of Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, the flaky titanium polyester catalyst is in a lamellar structure, and the thickness of the lamellar is 100-200 nm;
the preparation method of the sheet titanium polyester catalyst comprises the following steps: taking terephthalic acid or terephthalate, titanate and dihydric fatty alcohol as raw materials, carrying out reaction in stages under the conditions that the temperature is 150-280 ℃ and the pressure is 0.01-0.4 MPa, specifically comprising the steps of controlling the temperature to react for 0.5-2.0 h under the condition that the temperature is 150-250 ℃, then heating to 200-280 ℃ to continue the reaction, stopping the reaction when the degree of esterification or ester exchange reaches 70-90%, filtering while hot, and crushing and grinding the obtained solid product to prepare the sheet-shaped titanium polyester catalyst;
the terephthalic acid ester is dimethyl terephthalate, diethyl terephthalate, dihydroxyethyl terephthalate, dihydroxypropyl terephthalate or dihydroxybutyl terephthalate; the titanate is n-butyl titanate, tetraisopropyl titanate or ethyl titanate; the dihydric fatty alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol;
the stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl octyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent (e.g., Issman chemical OB-1, Clainen, Germany, solvent blue 45, Ciba Irganox 1425, Ciba Irgamod 195, Germany) or a reddening agent (e.g., Poulvan OnColoredgeglo, Clariant, Germany, Red GFP).
The preparation method of the titanium-based polyester for the Persian is as follows: and melting and blending the solid polyester prepolymer with the polymerization degree of 5-30 with a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, and cooling to obtain a solid polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 hours.
The preparation method of the titanium-based polyester for the Persian is as follows: adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 5-30, uniformly stirring and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein the additive is a sheet titanium polyester catalyst, a stabilizer and a toner, the sheet titanium polyester catalyst, the stabilizer and the toner can be directly added, can also be added after being dispersed in dihydric alcohol, can also be partially added directly, and can be partially added after being dispersed in the dihydric alcohol, the adding modes are all within the protection range of the invention, when the adding mode is adopted after being dispersed in the dihydric alcohol, when the mass ratio of the polyester prepolymer to the dihydric alcohol is more than 1, the final product is in a solid state; when the mass ratio of the polyester prepolymer to the dihydric alcohol is 0.5-1, the final product is in a slurry state; the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
The preparation method of the titanium-based polyester for the Persian is as follows: a, B and C are mixed evenly and then are processed through esterification reaction, pre-polycondensation reaction and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is additive or dihydric alcohol dispersion liquid of the additive, the additive is sheet titanium polyester catalyst, stabilizer and toner, the sheet titanium polyester catalyst, the stabilizer and the toner can all adopt a direct adding mode, can also adopt a mode of adding the rest dihydric alcohol after being dispersed in the dihydric alcohol and then being supplemented, can also partly adopt a direct adding mode, and partly adopt a mode of adding the rest dihydric alcohol after being dispersed in the dihydric alcohol, and the adding modes are all within the protection scope of the invention. In the polyester synthesis process in the prior art, a sheet-shaped titanium polyester catalyst, a stabilizer and a toner are added before esterification reaction, and the sheet-shaped titanium polyester catalyst, the stabilizer and the toner are subjected to system environment changes such as temperature, pressure and the like, and physical and chemical reactions possibly occur among each other or between the sheet-shaped titanium polyester catalyst, the stabilizer and the toner and reaction monomers for preparing polyester, so that the catalytic activity of the sheet-shaped titanium polyester catalyst, the stabilizer and the toner is changed. The invention firstly introduces the sheet titanium polyester catalyst, the stabilizer and the toner into the synthesis process of the prepolymer to prepare a polyester titanium catalyst composite material system, and then introduces the polyester titanium catalyst composite material system into a polyester reaction system, and as the synthesis process of the prepolymer is similar to the esterification and polycondensation reaction of polyester synthesis, the catalytic activity and the efficiency of the polyester titanium catalyst composite material system can be further improved when the polyester titanium catalyst composite material system is used as a polyester catalyst after the esterification and pre-polycondensation reaction of the prepolymer; the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-30 min.
In the preparation method of the titanium-based polyester for the Posmann, when the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-2: 1, and the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-1.5, the final product is in a solid state, and when the molar ratio of the sum of the molar amounts of the diols in B and C to A is more than 1.5, the final product is in a slurry state; b is the same as the dihydric alcohol in the dihydric alcohol dispersion liquid of the additive, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the sheet titanium polyester catalyst accounts for 10-20% of the sum of the mass of the dihydric alcohol in B and the glycol in C;
the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalate, the dibasic ester is dimethyl terephthalate, and the dihydric alcohol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
The titanium-based polyester for the Persian is prepared by the preparation method of the titanium-based polyester for the Persian, and mainly comprises modified polyester molecular chains and sheet-shaped titanium-based polyester catalysts dispersed among the modified polyester molecular chains, wherein the modified polyester molecular chains mainly comprise PTA chain segments, EG chain segments, SIPE chain segments and aliphatic binary chain segments.
Has the advantages that:
(1) according to the preparation method of the titanium-based polyester for the Possian fibers, the polyester prepolymer with the polymerization degree of 5-30 is used for wrapping the catalyst, and the catalyst is only melted at a high temperature and released in the polyester synthesis process, so that the secondary agglomeration phenomenon of the catalyst in the transportation or storage process can be avoided;
(2) according to the preparation method of the titanium-based polyester for the Possian fibers, the polyester prepolymer with the polymerization degree of 5-30 is used for wrapping the catalyst, the polyester prepolymer is an intermediate for preparing the polyester high polymer, and the polyester prepolymer has intrinsic good compatibility with an intermediate system for synthesizing the high polymer, so that the catalyst can show high dispersibility in the polyester synthesis process;
(3) according to the preparation method of the titanium-based polyester for the Persian, the polyester prepolymer with the polymerization degree of 5-30 is adopted to wrap the catalyst, so that the influence of SIPE on the catalyst is avoided, and the catalyst is ensured to have higher catalytic activity;
(4) the preparation method of the titanium-based polyester for the Persian is simple in process and convenient and fast to operate;
(5) the titanium-based polyester prepared by the preparation method of the titanium-based polyester for the Persian has excellent performance, meets the environmental protection requirement and has good application prospect.
Drawings
FIG. 1 is an infrared spectrum (FTIR spectrum) of a composite system of the polyester titanium based catalyst of example 7 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a sheet titanium polyester catalyst comprises the steps of mixing terephthalic acid, ethylene glycol and n-butyl titanate with a molar ratio of 1:1.5:0.01, reacting for 0.5h at 150 ℃ and under 0.01MPa, heating to 200 ℃, continuing to react until the esterification degree reaches 70%, terminating the reaction, filtering while hot, and crushing and grinding to obtain the sheet titanium polyester catalyst with the average particle size of 0.5 mu m.
Examples 2 to 6
A process for preparing the flaky Ti-series polyester catalyst includes such steps as mixing BT, CT and DT in mole ratio AT, reacting GT AT ET and FT, heating to HT, reacting until the esterification degree reaches IT, filtering, and pulverizing.
Example 7
A preparation method of a polyester titanium catalyst composite material system comprises the steps of firstly adding ethylene glycol dispersion liquid of a sheet-shaped titanium polyester catalyst with the mass concentration of 30 wt% into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of 5-8, and then uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the sheet-shaped titanium polyester catalyst is prepared from example 1, and the mass content of the sheet-shaped titanium polyester catalyst in the polyester titanium catalyst composite material system is 20 wt%.
0.1g of the polyester titanium catalyst composite system is dispersed in 30mL of water, after the mixture is heated and stirred for 3 hours at 70 ℃, the residual solid is washed by absolute ethyl alcohol and dried, and then the sample is subjected to FTIR characterization, as shown in figure 1, the crystal structure and characteristic groups of the sample of the polyester titanium catalyst composite system in the invention are not changed too much after the sample is treated by hot water, and the FTIR graph is also shown at 2924cm-1、2854cm-1Left and right CH2The vibration peak disappears, which indicates that the sample has better stability in water, and meanwhile, no stabilizer or toner is added in the above embodiment, so that the polyester titanium catalyst composite material system composed of the polyester prepolymer with the polymerization degree of 3-8 and the sheet titanium polyester catalyst has excellent stability.
Examples 8 to 12
A preparation method of a polyester titanium catalyst composite material system comprises the steps of firstly adding BN into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of AN, uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the BN contains additives, the additives comprise a titanium catalyst, a stabilizer and a toner, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are CN, DN and EN.
Example 13
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with the polymerization degree of 25-30, a sheet-shaped titanium polyester catalyst (catalyst), triisopropyl phosphate (stabilizer) and Germany Ciba Irganox 1425 (toner) at the temperature of 150 ℃ for 2 hours, cooling and crushing to obtain the polyester titanium catalyst composite material system, wherein the sheet-shaped titanium polyester catalyst is prepared from example 2, and the mass contents of the sheet-shaped titanium polyester catalyst, the triisopropyl phosphate and the Germany Ciba Irganox 1425 in the polyester titanium catalyst composite material system are respectively 18 wt%, 5 wt% and 4 wt%.
Examples 14 to 19
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with polymerization degree of AS with a titanium catalyst, a stabilizer and a toner at the temperature of BS (styrene-butadiene-styrene) for CS, cooling and crushing to obtain the solid polyester titanium catalyst composite material system, wherein the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are DS, ES and FS respectively.
Examples 20 to 24
A preparation method of a polyester titanium catalyst composite material system comprises the steps of uniformly mixing A, B and C, and then carrying out esterification reaction, pre-polycondensation reaction and cooling to obtain the polyester titanium catalyst composite material system, wherein A is dibasic acid (terephthalic acid, isophthalic acid or isophthalic acid-5-sodium sulfonate) or dibasic acid ester (dimethyl terephthalate), B is dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, the additive is a titanium catalyst, a stabilizer and a toner, the molar ratio of the sum of the molar amounts of the dihydric alcohol in the B and the dihydric alcohol in the C to the molar amount of the dihydric alcohol in the A is 1-2: 1, B is the same as the dihydric alcohol in the glycol dispersion liquid of the additive (specifically ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol), the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the titanium catalyst accounts for 10-20% (D) of the sum of the mass of the dihydric alcohol in the B and the dihydric alcohol in the C, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, the time is 2.0-2.5 h, the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, the time is 10-50 min, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are respectively 0.5-20 wt% (E), 5-15 wt% (F) and 0.5-8 wt% (G).
Examples 25 to 42
The titanium-based polyester for the Posman is prepared by adopting the polyester titanium-based catalyst composite material system prepared in the embodiment X, and the specific steps are as follows:
(1) mixing PTA, EG and a polyester titanium catalyst composite material system, and then carrying out esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure (P3) is 200-300 KPa, the temperature (T3) is 245-255 ℃, and the time (T3) is 3-4 h; wherein the molar ratio (molar ratio 2) of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium polyester catalyst contained in the polyester titanium catalyst composite material system in the esterification reaction process is 8-13 ppm of the theoretical mass (titanium content) of the titanium-based polyester for the Posman in terms of the mass of titanium element;
(2) carrying out copolymerization modification on the esterified oligomer, SIPE and aliphatic dibasic acid (A) to obtain a copolymerization modified esterified substance, wherein the reaction pressure (P4) is 10-100 KPa, the temperature (T4) is 230-250 ℃, and the time (T4) is 1-1.5 h; wherein the addition amount of SIPE is 50-70 wt% of the addition amount of EG (addition amount 1) in the step (1), and the addition amount of aliphatic dibasic acid is 3-5 wt% of the addition amount of EG (addition amount 2) in the step (1);
(3) pre-polycondensation reaction is carried out on the copolymerization modified esterified product to obtain a pre-polycondensation product, wherein the pressure (P5) of the pre-polycondensation reaction is 1-2 KPa, the temperature (T5) is 250-260 ℃, and the time (T5) is 0.5-1 h;
(4) carrying out final polycondensation on the pre-polycondensation product to obtain a titanium-based polyester melt for the Podlon, wherein the pressure (P6) of the final polycondensation reaction is 50-100 Pa, the temperature (T6) is 260-270 ℃, and the time (T6) is 1.5-2.5 h; wherein the intrinsic viscosity of the titanium-based polyester melt for the Possian is 0.38-0.40 dL/g, the chroma L value of the titanium-based polyester for the Possian is 88-90, and the b value is 5-6;
(5) and cooling and dicing the polyester melt with the titanium-based polyester to obtain the polyester chips with the titanium-based polyester for the polystyrene.
The parameters of examples 25 to 42 are shown in Table 1-2 below.
Example 43
A titanium-based polyester for Posmann and a preparation method thereof are basically the same as the polyester in the example 25, except that the polyester titanium-based catalyst composite system in the step (1) and the addition amount thereof are changed to be added in the step (3), and specific parameters are shown in a table 2.
Table 1 parameters corresponding to examples 25 to 34
TABLE 2 parameters corresponding to examples 35 to 43
Claims (10)
1. A preparation method of titanium-based polyester for Posmann is characterized by comprising the following steps: mixing PTA, EG, SIPE, aliphatic dibasic acid and a polyester titanium catalyst composite material system, and then carrying out esterification reaction and polycondensation reaction to obtain titanium-based polyester for the Possian;
the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30 and a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer.
2. The method for preparing titanium-based polyester for Persian being in accordance with claim 1, comprising the following steps:
(1) mixing PTA, EG and a polyester titanium catalyst composite material system, and then carrying out esterification reaction to obtain an esterification oligomer, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 200-300 KPa, the temperature is 245-255 ℃, and the time is 3-4 h;
(2) carrying out copolymerization modification on the esterified oligomer, SIPE and aliphatic dibasic acid to obtain a copolymerization modified esterified substance, wherein the reaction pressure is 10-100 KPa, the temperature is 230-250 ℃, and the reaction time is 1-1.5 h;
(3) pre-polycondensation reaction is carried out on the copolymerization modified esterified product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 2-1 KPa, the temperature is 250-260 ℃, and the time is 0.5-1 h;
(4) carrying out final polycondensation on the pre-polycondensation product to obtain a titanium-based polyester melt for the Podlon, wherein the pressure of the final polycondensation reaction is 50-100 Pa, the temperature is 260-270 ℃, and the time is 1.5-2.5 h;
(5) and cooling and dicing the polyester melt with the titanium-based polyester to obtain the polyester chips with the titanium-based polyester for the polystyrene.
3. The preparation method of the titanium-based polyester for the Posman according to claim 2, wherein in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of the sheet-shaped titanium-based polyester catalyst contained in the polyester titanium-based catalyst composite material system in the esterification reaction process is 8-13 ppm of the theoretical mass of the titanium-based polyester for the Posman based on the mass of titanium element;
in the step (2), the addition amount of SIPE is 50-70 wt% of the addition amount of EG in the step (1), the addition amount of aliphatic dibasic acid is 3-5 wt% of the addition amount of EG in the step (1), and the aliphatic dibasic acid is more than one of oxalic acid, malonic acid, succinic acid, adipic acid and sebacic acid;
in the step (4), the intrinsic viscosity of the titanium-based polyester melt for the Persian is 0.38-0.40 dL/g, the chroma L value of the titanium-based polyester for the Persian is 88-90, and the b value is 5-6.
4. The method for preparing the titanium-based polyester for the Poulon according to claim 1, wherein the polyester prepolymer further contains a stabilizer and a toner, and the mass contents of the sheet-shaped titanium-based polyester catalyst, the stabilizer and the toner in the polyester titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%.
5. The method of claim 4, wherein the titanium-based polyester catalyst is Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, and the flaky titanium polyester catalyst has a lamellar structure;
the stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl octyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent or a reddening agent.
6. The method for preparing titanium-based polyester for Persian being claimed in claim 5, wherein the method for preparing the polyester titanium-based catalyst composite material system comprises: and melting and blending the solid polyester prepolymer with the polymerization degree of 5-30 with a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, and cooling to obtain the polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 h.
7. The method for preparing titanium-based polyester for Persian being claimed in claim 5, wherein the method for preparing the polyester titanium-based catalyst composite material system comprises: adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 5-30, uniformly stirring and cooling to obtain a polyester titanium catalyst composite material system, wherein the additive is a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
8. The method for preparing titanium-based polyester for Persian being claimed in claim 5, wherein the method for preparing the polyester titanium-based catalyst composite material system comprises: a, B and C are uniformly mixed and then subjected to esterification reaction, pre-polycondensation reaction and cooling to obtain a polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, the additive is a sheet-shaped titanium polyester catalyst, a stabilizer and a toner, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2-2.5 hours; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-30 min.
9. The method for preparing the titanium-based polyester for the Poslin fiber as claimed in claim 8, wherein the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-2: 1, B is the same as the diol in the diol dispersion liquid of the additive, the mass concentration of the diol dispersion liquid of the additive is 35-70 wt%, and the mass of the sheet-shaped titanium-based polyester catalyst accounts for 10-20% of the sum of the mass of the diols in B and C;
the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalate, the dibasic ester is dimethyl terephthalate, and the dihydric alcohol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
10. The titanium-based polyester for Persian being prepared by the method for preparing the titanium-based polyester for Persian according to any one of claims 1 to 9, wherein the method comprises the following steps: the modified polyester catalyst mainly comprises modified polyester molecular chains and a flaky titanium polyester catalyst dispersed among the modified polyester molecular chains, wherein the modified polyester molecular chains mainly comprise PTA chain segments, EG chain segments, SIPE chain segments and aliphatic binary chain segments.
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